KR20000029050A - aluminium electrolytic condenser - Google Patents

aluminium electrolytic condenser Download PDF

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KR20000029050A
KR20000029050A KR1019990044421A KR19990044421A KR20000029050A KR 20000029050 A KR20000029050 A KR 20000029050A KR 1019990044421 A KR1019990044421 A KR 1019990044421A KR 19990044421 A KR19990044421 A KR 19990044421A KR 20000029050 A KR20000029050 A KR 20000029050A
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ammonium
acid
phosphate
electrolytic capacitor
electrolyte
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KR1019990044421A
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KR100423196B1 (en
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쯔바키유이찌로
마쯔우라히로유키
모로쿠마무네히로
미나토코이찌로
닛타유키히로
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모리시타 요이찌
마쯔시다덴기산교 가부시키가이샤
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004Details
    • H01G9/02Diaphragms; Separators
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004Details
    • H01G9/022Electrolytes; Absorbents

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  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)
  • Fixed Capacitors And Capacitor Manufacturing Machines (AREA)

Abstract

PURPOSE: An aluminum electrolytic condenser is provided to elevate reliability by preventing the transformation of the appearance despite of long use at high temperature and the degradation of property and by eliminating an ignition point. CONSTITUTION: An electrolytic condenser contains 20-90wt% of moisture content of electrolyte. Herein, the electrolyte contains at least one of compounds selected from ammonium formate, ammonia lactate, ammonium glycol, ammonium oxalate, ammonium succinate, ammonium malonic acid, ammonium adipate, ammonium benzoate, ammonium glutaric acid, and ammonium azelaic acid as main electrolyte. And, the electrolyte includes more than 1wt% of compound selected from organic carboxyl acid of a certain structure and ammonium chloride thereof. The condensing point of the electrolyte is under 10°C below zero point. The content of chlorine in the sealing agent of the condenser is under 300ppm to the weight of the sealing agent. The electrolytic condenser is formed by interposing a separator(4) between an anode foil(2) and a cathode foil(3) for impregnating electrolyte for driving. Then, the separator is inserted into an aluminum case(5) for sealing the aperture of the aluminum case by using a rubber sealing agent(6).

Description

알루미늄전해콘덴서{aluminium electrolytic condenser}Aluminum electrolytic condenser

본 발명은 비인화점의 전해액을 사용한, 저온특성에 뛰어나고, 고온하에서 장시간 사용했을 경우라도 외관변화, 특성열악화가 적은 신뢰성이 높은 알루미늄전해콘덴서(이하 전해콘덴서라함)에 관한 것이다.The present invention relates to a highly reliable aluminum electrolytic capacitor (hereinafter referred to as an electrolytic capacitor) that is excellent in low-temperature characteristics using an electrolyte of a non-flash point and has little appearance change and deterioration in characteristics even when used for a long time at a high temperature.

종래의 전해콘덴서는 도 1에 표시한 바와 같이, 양극박(2)과 음극박(3)의 사이에 마닐라삼, 크라프트지 등의 세퍼레이터(4)를 개재시킨 상태에서 두루감은것에, 구동용 전해액(이하 전해액이라함)을 함침시켜서 알루미늄케이스(5)에 삽입한 후, 알루미늄케이스(5)의 개구부를 고무제의 봉구재(6)에 의해 봉구함으로써 구성되어 있다. 양극박(2)은 알루미늄박을 에칭처리에 의해 표면확대화(조면(粗面)화)처리후, 양극산화처리에 의해 유전체층을 형성한 것이다.As shown in FIG. 1, the conventional electrolytic capacitor is wound around the separator foil 4 such as Manila hemp and kraft paper between the positive electrode foil 2 and the negative electrode foil 3, and the driving electrolyte solution. After impregnating (hereinafter referred to as electrolyte solution) and inserting it into the aluminum case 5, the opening of the aluminum case 5 is sealed by a sealing member 6 made of rubber. The positive electrode foil 2 is a dielectric layer formed by anodizing after surface enlargement (roughening) the aluminum foil by etching.

상기 전해액은 조면화된 양극박(2)에 밀착함으로써 정전(靜電)용량을 발생한다. 또 전해액은 그 지닌화성능력에 의해 알루미늄산화피막의 유전체층을 보수할 수 있기 때문에, 누설전류를 낮게 유지할 수 있는 등의 기능을 담당하고 있다. 또, 전해액이 지닌 특성중에서도 특히 전기전도도는 전해콘덴서의 임피던스성능에 큰영향을 미친다.The electrolyte is in close contact with the roughened positive electrode 2 to generate an electrostatic capacity. In addition, since the electrolyte solution can repair the dielectric layer of the aluminum oxide film by its carrying capacity, it is responsible for maintaining a low leakage current. In addition, among the properties of the electrolyte, the electrical conductivity has a great influence on the impedance performance of the electrolytic capacitor.

이상의 관점에서, 특히 보증온도 105℃이상, 정격전압100V이하의 저압급이고 또한, 저임피던스의 전해콘덴서에는, 저온특성과 화성성에 뛰어나는 γ-부틸로락톤을 용매로하고, 프탈산이나 말레산의 4급암모늄염을 전해질로하는 전기전도도가 높은, 고온속에서도 안정적인 전해액이 사용되어 왔다. (일본국 특개소 62-145713호 공보, 동특개소 62-145715호 공보참조)In view of the above, the low-pressure and low-impedance electrolytic capacitors having a guaranteed temperature of 105 ° C. or higher and a rated voltage of 100 V or lower, and γ-butylolactone excellent in low temperature characteristics and chemical conversion are used as solvents. A stable electrolyte has been used even at a high temperature with high electrical conductivity using a quaternary ammonium salt as an electrolyte. (See Japanese Patent Application Laid-Open No. 62-145713 and Japanese Patent Application Laid-Open No. 62-145715)

그러나 상기 γ-부틸로락톤용매에 프탈산이나 말레산의 4급암모늄염을 용해한 전해액을 사용한 전해콘덴서를, 습도가 높은 분위기하에서 연속통전사용했을 경우, 음극부에서 강알칼리화합물이 생성된다. 이 강알칼리화합물은 특히 음극리드나 그것에 접하는 봉구재(6)를 침식하기 때문에, 콘덴서외부에 전해액이 누출한다고하는 문제가 일어나는 경우가 있었다.However, when the electrolytic capacitor using the electrolyte solution which melt | dissolved the quaternary ammonium salt of phthalic acid or maleic acid in the said (gamma)-butyrolactone solvent is used for continuous energization in an environment with high humidity, a strong alkali compound is produced | generated at a negative electrode part. In particular, this strong alkaline compound erodes the cathode lead and the sealing material 6 in contact with it, so that there is a problem that an electrolyte solution leaks outside the capacitor.

이와 같은 문제를 회피하기위해서는, 알칼리화합물생성이 적은 전해액, 즉 에틸렌글리콜 및 물을 용매로하고, 아디프산암모늄등의 암모늄염을 전해질로한 전해액을 사용하는 것이 유효하다.In order to avoid such a problem, it is effective to use an electrolyte solution having low alkali compound generation, that is, an electrolyte solution containing ethylene glycol and water as a solvent and an ammonium salt such as ammonium adipic acid as an electrolyte.

또, γ-부틸로락톤용매를 사용한 전해액은 100℃전후의 인화점을 지니기때문에, 전자기기의 이상 동작등에 의해 전해액이 분출했을때에도 발화의 위험성이 없다고는 단언할 수 없었다.In addition, since the electrolyte solution using the γ-butyrolactone solvent has a flash point around 100 ° C, there is no assertion that there is no risk of ignition even when the electrolyte is ejected due to abnormal operation of the electronic device.

한편, 보증온도 85℃이고 정격전압 100V이하의 저압급의 전해콘덴서에 있어서는, 전해액의 용매에 에틸렌글리콜과 물과의 혼합용매를 사용하고, 아디프산암모늄 등의 암모늄염을 전해질로하는 전해액을 사용할 수 있다. 물은 전기전도도를 높이는 것을 목적으로 첨가된다. 이런 종류의 전해액을 사용한 전해콘덴서에 있어서는, 용매성분의 하나인 물의 비등점(100℃)이상의 온도에서 장기간전기성능을 유지하는 것이 곤란하다. 예를 들면, 온도 110℃의 정격전압인가시험에 있어서는, 알루미늄과 물과의 반응의 결과 발생하는 다량의 수소가스가 발생한다. 이 영향에 의한 내압상승때문에, 알루미늄케이스바닥면부분의 안전밸브가 작동하는 경우가 있다. 또, 온도 110℃의 무부하방치시험에 있어서는, 1000시간이내에 시험후의 누설전류치의 변화율이 +5000%를 넘는 등의 불편이 발생하고 있었다.On the other hand, in a low pressure electrolytic capacitor having a guaranteed temperature of 85 ° C. and a rated voltage of 100 V or less, a mixed solvent of ethylene glycol and water is used as a solvent of an electrolyte solution, and an electrolyte solution containing ammonium salts such as ammonium adipic acid as an electrolyte is used. Can be. Water is added for the purpose of increasing the electrical conductivity. In electrolytic capacitors using this type of electrolyte, it is difficult to maintain long-term electrical performance at temperatures above the boiling point (100 ° C.) of water, which is one of the solvent components. For example, in a rated voltage application test with a temperature of 110 ° C., a large amount of hydrogen gas generated as a result of the reaction between aluminum and water is generated. Due to this increase in internal pressure, the safety valve at the bottom of the aluminum case may operate. Moreover, in the no load leaving test at a temperature of 110 ° C., inconveniences such as the rate of change of the leakage current value after the test exceeded + 5000% occurred within 1000 hours.

이들 문제를 해결하기 위해, 전극박과 물과의 반응을 억제할 목적으로 전해액에 여러가지의 인(燐)계화합물을 첨가하는 방법이나, 발생한 수소가스를 흡수할 목적으로 여러가지의 니트로화합물을 첨가하는 등의 방법이 제안되고 있다. 이들 방법을 사용해도 정격전압 100V이하의 콘덴서에 있어서는, 함수율이 20%를 넘게되는 고함수율의 전해액을 사용해서, 100℃이상의 온도에 있어서 장기간 콘덴서의 전기성능을 유지하는 것은 곤란하였다.In order to solve these problems, a method of adding various phosphorus compounds to the electrolyte for the purpose of suppressing the reaction between the electrode foil and water, or adding various nitro compounds for the purpose of absorbing the generated hydrogen gas. And the like have been proposed. Even if these methods were used, it was difficult to maintain the electrical performance of the capacitor for a long time at a temperature of 100 ° C. or more using a high moisture content electrolyte solution having a water content of more than 20% in a capacitor having a rated voltage of 100 V or less.

또한, 함수율이 20%이상의 전도도가 높은 전해액을 100℃이상의 온도에서 장기간 사용하는 경우에는, 함수율이 20%미만의 저함수율의 전해액에서는 문제가 되지 않했던 봉구고무속의 염소가 문제가 된다. 즉, 장기간의 고온속부하시험에 있어서 양극알루미늄리드의 부식이 발생하고, 결과로서 누설전류가 증대하거나, 양극알루미늄리드의 부식단선을 초래하는 경우가 있었다.In addition, when the electrolyte having a high conductivity of 20% or more is used for a long time at a temperature of 100 ° C or more, chlorine in the sealing rubber, which has not been a problem in the electrolyte having a low moisture content of less than 20%, becomes a problem. That is, in the long-term high temperature load test, corrosion of the anode aluminum lead occurs, and as a result, leakage current may increase or lead to corrosion disconnection of the anode aluminum lead.

본 발명은 이와 같은 종래의 과제를 해결하고, 고신뢰성의 전해콘덴서를 제공하는 것을 목적으로 하는 것이다.An object of the present invention is to solve such a conventional problem and to provide a highly reliable electrolytic capacitor.

도 1은 본 발명의 일실시형태를 포함하는 전해콘덴서의 구성을 표시한 일부절개사시도1 is a partially cutaway perspective view showing the configuration of an electrolytic capacitor including an embodiment of the present invention.

[도면의 주요부분에 대한 부호의 설명][Explanation of symbols on the main parts of the drawings]

2: 양극박(箔) 3: 음극박2: anode foil 3: cathode foil

4: 세퍼레이터 5: 알루미늄케이스4: Separator 5: Aluminum Case

6: 봉구재(封口材)6: sewing materials

본 발명의 전해콘덴서는, 전해액의 함수율이 20∼90wt%이고, 또한 전해액이 포름산암모늄, 아세트산암모늄, 락트산암모늄, 글리콜산암모늄, 옥살산암모늄, 숙신산암모늄, 말론산암모늄, 아디프산암모늄, 벤조산암모늄, 글루타르산암모늄, 아젤라산암모늄으로부터 선택되는 1종이상의 화합물을 주전해질로서 함유하고, 또한 트리메틸아디프산, 1,6-데칸디카르복시산, 세바스산, 1,7-옥탄디카르복시산, 부틸옥탄디카르복시산, 3-tert-부틸아디프산, 3-tert-옥틸헥산2산, 3-n-도데실헥산2산, (화합물1)로 표시되는 유리카르복시산, (화합물2)로 표시되는 유리카르복시산 또는 이들 유기산의 암모늄염으로부터 선택되는 1종이상의 화합물을 1wt%이상함유하는 것이다.The electrolytic capacitor of the present invention has a water content of 20 to 90 wt%, and the electrolyte solution is ammonium formate, ammonium acetate, ammonium lactate, ammonium glycolate, ammonium oxalate, ammonium succinate, ammonium malonate, ammonium adipic acid or ammonium benzoate. Containing at least one compound selected from ammonium glutarate and ammonium azelaate as the main electrolyte, and also trimethyladipic acid, 1,6-decanedicarboxylic acid, sebacic acid, 1,7-octanedicarboxylic acid, butyloctane Dicarboxylic acid, 3-tert-butyladipic acid, 3-tert-octylhexanoic acid, 3-n-dodecylhexanoic acid, free carboxylic acid represented by (Compound 1), free carboxylic acid represented by (Compound 2) Or 1 wt% or more of at least one compound selected from the ammonium salts of these organic acids.

(화합물1)(Compound 1)

단, R2는 저급알킬기, R1은 수소원자, 또는 다음의 기Provided that R 2 is a lower alkyl group, R 1 is a hydrogen atom, or

(화합물2)(Compound 2)

단, R3, R4는 저급알킬기, R5는 페닐기Provided that R 3 and R 4 are lower alkyl groups and R 5 is a phenyl group

본 발명의 전해액은 인화점을 지니지않고, 또한 응고점이 -10℃이하이다. 또, 본 발명의 전해콘덴서는 봉구재의 함유염소량이 봉구재중량에 대해서 300ppm이하이고, 또한 20℃, 100㎑에 있어서의 임피던스에 대한 -10℃, 100㎑의 임피던스비가 4이하인 정격전압 100V이하의 것이다. 본 발명에 의해, 신뢰성이 높고, 전해액이 분출했을때에도 발화의 위험성이 적은, 임피던스성능 및 저온특성에 뛰어난 정격전압 100V이하의 알루미늄전해콘덴서를 실현할 수 있다.The electrolyte solution of the present invention does not have a flash point and has a freezing point of -10 deg. In the electrolytic capacitor of the present invention, the chlorine content of the sealing material is 300 ppm or less with respect to the weight of the sealing material, and the impedance ratio of -10 ° C and 100 Hz to the impedance at 20 ° C and 100 Hz is 4 or less. will be. According to the present invention, it is possible to realize an aluminum electrolytic capacitor having a rated voltage of 100 V or less, which is high in reliability and has a low risk of ignition even when an electrolyte is ejected, and excellent in impedance performance and low temperature characteristics.

이하, 본 발명의 실시형태에 대해서 설명한다.EMBODIMENT OF THE INVENTION Hereinafter, embodiment of this invention is described.

본 발명의 전해콘덴서는, 표면에 산화알루미늄으로 이루어진 유전체층을 형성한 양극알루미늄박과 음극알루미늄박을 그 사이에 세퍼레이터를 개재시켜서 두루감음으로써 구성된 콘덴서소자에 전해액을 함침하고, 알루미늄케이스에 수납한 후, 알루미늄케이스의 개구부를 봉구재에 의해 봉하여 막은 것이다.The electrolytic capacitor of the present invention is impregnated with an electrolytic solution in a condenser element formed by winding a cathode aluminum foil and a cathode aluminum foil having a dielectric layer made of aluminum oxide on the surface with a separator therebetween, and then stored in an aluminum case. The opening of the aluminum case is sealed with a sealing material and closed.

본 발명에 관한, 전해액의 함수율은 20∼90wt%이다. 본 전해액은 포름산암모늄, 아세트산암모늄, 락트산암모늄, 글리콜산암모늄, 옥살산암모늄, 숙신산암모늄, 말론산암모늄, 아디프산암모늄, 벤조산암모늄, 글루타르산암모늄, 아젤라산암모늄으로부터 선택되는 1종이상의 화합물을 「주전해질」로서 함유하고, 또한 트리메틸아디프산, 1,6-데칸디카르복시산, 세바스산, 1,7-옥탄디카르복시산, 부틸옥탄디카르복시산, 3-tert-부틸아디프산, 3-tert-옥틸헥산2산, 3-n-도데실헥산2산, (화합물1)로 표시되는 유기카르복시산, (화합물2)로 표시되는 유기카르복시산 또는 이들 유기산의 암모늄염으로부터 선택되는 1종이상의 화합물(이하, 반응억제제)을 1wt%이상함유하고 있다. 또, 본 발명의 전해액은 인화점을 지니지 않는 것이며, 또한 구동용전해액의 응고점이 -10℃이하이다.The moisture content of electrolyte solution which concerns on this invention is 20-90 wt%. The electrolyte solution contains at least one compound selected from ammonium formate, ammonium acetate, ammonium lactate, ammonium glycolate, ammonium oxalate, ammonium succinate, ammonium malonate, ammonium adipic acid, ammonium benzoate, ammonium glutarate, and ammonium azelaate. It contains as a "main electrolyte", and also trimethyl adipic acid, 1,6-decanedicarboxylic acid, sebacic acid, 1,7-octanedicarboxylic acid, butyloctanedicarboxylic acid, 3-tert- butyladipic acid, 3-tert At least one compound selected from -octylhexanoic acid, 3-n-dodecylhexanoic acid, an organic carboxylic acid represented by (Compound 1), an organic carboxylic acid represented by (Compound 2), or an ammonium salt of these organic acids (hereinafter, Reaction inhibitors) 1 wt% or more. In addition, the electrolyte solution of the present invention does not have a flash point, and the solidification point of the driving electrolyte is -10 deg.

또, 본 발명의 전해콘덴서는 정격전압 100V이하의 것이고, 20℃100㎑에 있어서의 임피던스에 대한 -10℃, 100㎑의 임피던스비가 4이하이다.The electrolytic capacitor of the present invention has a rated voltage of 100 V or less, and an impedance ratio of -10 ° C. and 100 Hz to an impedance at 20 ° C. 100 Hz is 4 or less.

또한, 전해액의 함수율이 20%미만의 범위에서는 저온에서의 전기도전도가 불충분하다. 이때문에, 20℃, 100㎑에 있어서의 임피던스에 대한 -10℃, 100㎑의 임피던스비가 4를 초과하므로 바람직하지 않다. 또 함수율이 90%를 넘는 범위에서는, 전해액의 응고점이 -10℃보다 높은 온도가 되는 경우가 있다. 이 때문에, 상기한 20℃에서의 임피던스성능을 확보할 수는 있으나, 콘덴서의 저온쪽에서의 보증온도범위가 -10℃이상으로 되어 보증범위가 좁아지므로 바람직하지 않다.Moreover, in the range whose water content of electrolyte solution is less than 20%, electrical conductivity in low temperature is inadequate. For this reason, since the impedance ratio of -10 degreeC and 100 Hz to the impedance in 20 degreeC and 100 Hz is more than 4, it is unpreferable. Moreover, in the range whose moisture content exceeds 90%, the solidification point of electrolyte solution may become temperature higher than -10 degreeC. For this reason, although the impedance performance at 20 degreeC mentioned above can be ensured, since the guaranteed temperature range in the low temperature side of a capacitor becomes more than -10 degreeC and a guarantee range becomes narrow, it is not preferable.

또, 상기 반응억제제는, 전극박표면에 흡착하여, 물과의 반응을 저해하는 것이며, 특히 고온속부하의 상태에서의 효과가 크다. 또, 이들 유기카르복시산 성분의 함유율이 1wt%이하의 범위에 있어서는 양극박보호의 효과가 극단적으로 약해지므로 바람직하지 않다.In addition, the reaction inhibitor is adsorbed on the surface of the electrode foil to inhibit the reaction with water, and in particular, the effect in the state of high temperature speed load is large. Moreover, since the effect of anodic foil protection becomes extremely weak in the content rate of these organic carboxylic acid components being 1 weight% or less, it is unpreferable.

또, 본 발명의 봉구재의 함유염소량은 봉구재중량에 대해서 300ppm이하이다. 함유염소량이 봉구재중량에 대해서 300ppm을 초과하는 봉구재를 사용해서 콘덴서를 구성하면, 100℃이상의 온도에 있어서 정격전압시험을 행하였을때에, 봉구고무로부터 추출된 염화물이 이온으로 해리(解離)되고, 그 결과, 고온하에서 양극알루미늄리드를 부식시키므로 바람직하지 않다.Moreover, the amount of chlorine contained in the sealing material of this invention is 300 ppm or less with respect to the sealing material weight. If the chlorine content of the condenser is composed of a sealing material of more than 300 ppm relative to the weight of the sealing material, the chloride extracted from the sealing rubber dissociates into ions when the rated voltage test is performed at a temperature of 100 ° C or higher. As a result, the anode aluminum lead is corroded under high temperature, which is not preferable.

또, 본 발명의 전해콘덴서는 온도 100℃이상에서의 정격전압부하 및 무부하방치시험에 있어서의 1000시간이내의 알루미늄케이스바닥면부분의 밸브팽장량이 +1㎜이내이다. 또, 100℃이상에서 무부하방치시험을 실시한 1000시간이내에서의 누설전류치의 변화율이 초기누설전류치에 대해서 +5000%이내이다. 알루미늄케이스바닥면부분의 밸브팽창량이 1㎜이상, 및 무부하방치시험 1000시간이내에서의 누설전류치의 변화율이 +5000%이상으로되면 제품외관 및 특성에 현저한 변화를 미치기때문에 바람직하지 않다.In addition, the electrolytic capacitor of the present invention has a valve expansion amount of +1 mm in the bottom portion of the aluminum casing within 1000 hours in a rated voltage load and a no-load standing test at a temperature of 100 ° C. or higher. In addition, the rate of change of the leakage current value within 1000 hours of the no-load standing test at 100 ° C or higher is within + 5000% of the initial leakage current value. When the expansion ratio of the leakage current value in the aluminum casing bottom portion of 1 mm or more and within 1000 hours of no load unloading test becomes + 5000% or more, it is not preferable because it causes a significant change in product appearance and characteristics.

이하, 본 발명의 구체적인 재료와, 배합비율에 대해서 설명한다.Hereinafter, the specific material and compounding ratio of this invention are demonstrated.

본 발명에 관한 전해액은, 알콜류, 다가알콜류, 폴리에틸렌글리콜, 에틸렌옥사이드와 프로필렌옥사이드로 이루어진 공중합물로부터 선택되는 1종이상으로 이루어진 유기용매를 함유하고, 주전해질과 반응억제제와, 알킬인산에스테르, 차아인산, 피로인산 및 이들의 염으로부터 선택되는 1종이상의 인화화합물을 0.01wt%이상 함유하고, 또한 p-니트로페놀, m-니트로페놀, o-니트로페놀, p-니트로벤조산, m-니트로벤조산, o-니트로벤조산, p-니트로아니솔, m-니트로아니솔, o-니트로아니솔로부터 선택되는 1종이상의 니트로화합물을 0.01wt%이상 함유하는 것이다.The electrolyte solution according to the present invention contains an organic solvent composed of one or more selected from alcohols, polyhydric alcohols, polyethylene glycols, copolymers of ethylene oxide and propylene oxide, and contains a main electrolyte, a reaction inhibitor, an alkyl phosphate ester, and a tea. 0.01 wt% or more of at least one phosphorus compound selected from phosphorous acid, pyrophosphoric acid and salts thereof, and also contains p-nitrophenol, m-nitrophenol, o-nitrophenol, p-nitrobenzoic acid, m-nitrobenzoic acid, It contains 0.01 wt% or more of one or more nitro compounds selected from o-nitrobenzoic acid, p-nitroanisole, m-nitroanisole and o-nitroanisole.

사용하는 용매의 구체예로서는, 알콜류[1가알콜(부틸알콜, 디아세톤알콜, 벤조알콜, 아미노알콜등); 2가알콜(에틸렌글리콜, 폴리에틸렌글리콜, 프로필렌글리콜, 1,3-프로판디올, 1,2-부탄디올, 1,3-부탄디올, 1,4-부탄디올, 2,3-부탄디올, 1,5-펜탄디올, 2-메틸-2,4-펜탄디올, 2-에틸-1,3-헥산디올, 디에틸렌글리콜, 헥실렌글리콜, 페닐글리콜등); 3가알콜(글리세린, 폴리글리세린, 2-에틸-2-히드록시메틸-1,3-프로판디올, 1,2,6-헥산트리올, 3-메틸펜탄-1,3,5-트리올등);헥시톨등], 에테르류[모노에테르(에틸렌글리콜모노메틸에테르, 디에틸렌글리콜모노메틸에테르, 디에틸렌글리콜모노에틸에테르, 에틸렌글리콜모노페닐에테르등); 디에테르류(에틸렌글리콜디메틸에테르), 에틸렌글리콜디에틸에테르, 디에틸렌글리콜디메틸에테르, 디에틸렌글리콜디에틸에테르등)등], 또 에틸렌옥사이드와 프로필렌옥사이드로 이루어진 공중합물 및 이들 2종이상의 혼합물을 들 수 있다. 이중에서도 각종 용질(溶質)의 용해도가 높고, 온도특성에 뛰어난 에틸렌글리콜이 바람직하다.As a specific example of the solvent used, Alcohols [monohydric alcohol (butyl alcohol, diacetone alcohol, benzo alcohol, amino alcohol, etc.); Dihydric alcohols (ethylene glycol, polyethylene glycol, propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol , 2-methyl-2,4-pentanediol, 2-ethyl-1,3-hexanediol, diethylene glycol, hexylene glycol, phenyl glycol and the like); Trihydric alcohols (glycerine, polyglycerol, 2-ethyl-2-hydroxymethyl-1,3-propanediol, 1,2,6-hexanetriol, 3-methylpentane-1,3,5-triol, etc. Hexitol, etc.], Ethers (monoether (ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, ethylene glycol monophenyl ether, etc.)); Diethers (ethylene glycol dimethyl ether), ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, etc.), copolymers of ethylene oxide and propylene oxide, and mixtures of two or more thereof. Can be mentioned. Of these, ethylene glycol having high solubility in various solutes and excellent in temperature characteristics is preferable.

상기 전해액의 반응억제제의 배합비율은, 에틸렌글리콜을 용매로 했을 경우, 주전해질에 대해서 반응억제제의 총함유량의 비율이 0.05이상∼5.0미만의 범위에 있고, 또한 주전해질과 반응억제제의 총함유량이 전해액의 중량에 대해서 10wt%이상인 구성이 바람직하다. 상기 조성범위에 있어서, 이들 화합물의 전극박에 각각의 기능을 지니고서 흡착하여, 콘덴서특성을 손상하는 일없이 전극박과 물과의 수화(水和)반응을 억제할 수 있다.When the reaction ratio of the reaction inhibitor of the electrolyte solution is ethylene glycol as a solvent, the ratio of the total content of the reaction inhibitor to the main electrolyte is in the range of 0.05 or more and less than 5.0, and the total content of the main electrolyte and the reaction inhibitor It is preferable that the composition is 10 wt% or more with respect to the weight of the electrolyte solution. In the above composition range, the electrode foil of these compounds can be adsorbed with their respective functions to suppress the hydration reaction between the electrode foil and water without impairing the capacitor characteristics.

또, 전해액속에 알킬인산에스테르, 차아인산, 피로인산 및 이들의 암모늄염으로부터 선택되는 1종이상의 인화합물을 0.01wt%이상 함유시킴으로써, 이들 화합물이 전극박에 흡착하여, 콘덴서특성을 손상하는 일없이 전극박과 물과의 반응을 억제한다. 또, p-니트로페놀, m-니트로페놀, o-니트로페놀, p-니트로벤조산, m-니트로벤조산, o-니트로벤조산, p-니트로아니솔, m-니트로아니솔, o-니트로아니솔로부터 선택되는 1종이상의 니트로화합물은, 니트로기의 환원성에 의해 수소가스흡수의 역할을 다한다.In addition, by incorporating 0.01 wt% or more of one or more phosphorus compounds selected from alkyl phosphate esters, hypophosphorous acid, pyrophosphoric acid and ammonium salts thereof in the electrolyte solution, these compounds are adsorbed onto the electrode foil, without damaging the capacitor characteristics. Suppress the reaction of gourd and water. From p-nitrophenol, m-nitrophenol, o-nitrophenol, p-nitrobenzoic acid, m-nitrobenzoic acid, o-nitrobenzoic acid, p-nitroanisole, m-nitroanisole and o-nitroanisole At least one nitro compound to be selected plays a role of hydrogen gas absorption by reducing the nitro group.

상기 인화합물은, 특히 음극박쪽에 흡착되는 것이나, 상기 니트로화합물은 상기 반응억제제의 음극박에의 흡착효과를 더욱 높인다. 이들의 결과 상기 니트로화합물은, 음극박의 물에 대한 보호효과를 효율좋게 높일 수 있다. 이때의 니트로화합물의 농도는 전해액에 대해서 0.01wt%이상이 바람직하고, 0.01wt%이하에서는 병용의 효과가 손상된다.The phosphorus compound is particularly adsorbed on the negative electrode foil, but the nitro compound further enhances the adsorption effect of the reaction inhibitor on the negative electrode foil. As a result of these, the nitro compound can efficiently increase the protective effect against water of the negative electrode foil. At this time, the concentration of the nitro compound is preferably 0.01 wt% or more with respect to the electrolyte, and below 0.01 wt% impairs the combined effect.

또, 본 발명의 전해콘덴서는, 구성하는 세퍼레이터 또는 전극박의 어느한쪽에, 알킬인산에스테르, 차아인산, 피로인산으로부터 선택되는 1종이상의 화합물 또는 그염, 또는 일반식(화합물6)인 실리콘화합물 및 실란커플링제, 알콕시실란이 부착한 것이다.In addition, the electrolytic capacitor of the present invention has at least one compound selected from alkyl phosphate esters, hypophosphorous acid, pyrophosphoric acid, salts thereof, or a silicon compound of the general formula (Compound 6) on either the separator or the electrode foil. The silane coupling agent and the alkoxysilane adhered.

(화합물6)(Compound 6)

실리콘화합물로서는, 히드록시변성실리콘, 아미노변성실리콘, 카르복실변성실리콘, 알콜변성실리콘, 에폭시변성실리콘인 반응성실리콘 등을 들 수 있다. 일반식(화합물6)로 표시되는 실리콘화합물의 X1∼X6의 구체예로서는, 메틸기, 에틸기, 프로필기, 부틸기 등의 알킬기류, 비닐기, 알릴기 등의 알케닐기, 페닐기, 나프틸기 등의 아릴기, 벤질기, 페네틸기 등의 아랄킬기류 등의 탄화수소기, 메톡시기, 에톡시기, 프로폭시기, 부톡시기, 비닐옥시기, 페녹시기, 벤질옥시기 등의 옥시탄화수소기 또는 수산기를 들 수 있다. 다른예로서는, 메틸카르복실기, 에틸카르복실기, 프로필카르복실기 등의 지방족카르복실기 등을 들 수 있다. 또, 메틸아민기, 에틸아민기, 프로필아민기, 페닐아민기 등의 아미노탄화수소기 등을 들 수 있다. 사용되는 실리콘화합물은 이상으로 한정되는 일은 없으며, 일반적인 반응성실리콘화합물이라도 가능하다.Examples of the silicone compound include hydroxy-modified silicon, amino-modified silicon, carboxyl-modified silicon, alcohol-modified silicon, and reactive silicon which is epoxy-modified silicon. Specific examples of X 1 to X 6 of the silicone compound represented by General Formula (Compound 6) include alkyl groups such as methyl group, ethyl group, propyl group and butyl group, alkenyl groups such as vinyl group and allyl group, phenyl group and naphthyl group Hydrocarbon groups such as aralkyl groups such as aryl group, benzyl group and phenethyl group, oxyhydrocarbon group or hydroxyl group such as methoxy group, ethoxy group, propoxy group, butoxy group, vinyloxy group, phenoxy group and benzyloxy group Can be mentioned. As another example, aliphatic carboxyl groups, such as a methyl carboxyl group, an ethyl carboxyl group, and a propyl carboxyl group, etc. are mentioned. Moreover, amino hydrocarbon groups, such as a methylamine group, an ethylamine group, a propylamine group, and a phenylamine group, etc. are mentioned. The silicon compound to be used is not limited to the above, and may be a general reactive silicone compound.

또 실란커플링제로서는 N-β(아미노에틸)γ-아미노프로필트리메톡시실란, N-β(아미노에틸)γ-아미노프로필메틸디메톡시실란, N-β(아미노에틸)γ-아미노프로필트리에톡시실란, γ-글리시독시프로필트리메톡시실란, 비닐트리메톡시실란, 비닐트리에톡시실란, 비닐트리스(β메톡시에톡시실란), β-(3,4-에톡시시클로헥실)에틸트리메톡시실란, γ-글리시독시프로필메틸디에톡시실란, γ-글리시독시프로필메틸디에톡시실란, γ-메타클릴옥시프로필메틸디메톡시실란, γ-메타클릴옥시프로필메틸디에톡시실란, γ-아미노프로필트리에톡시실란, N-페닐-γ-아미노프로필트리메톡시실란, γ-메르캅토프로필트리메톡시실란 등이 있다. 알콕시실란으로서 테트라메톡시실란, 테트라에톡시실란 등이 있다.As the silane coupling agent, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane and N-β (aminoethyl) γ-aminopropyltrie Oxysilane, γ-glycidoxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (βmethoxyethoxysilane), β- (3,4-ethoxycyclohexyl) ethyl Trimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ -Aminopropyl triethoxysilane, N-phenyl- (gamma)-aminopropyl trimethoxysilane, (gamma)-mercaptopropyl trimethoxysilane, etc. are mentioned. Examples of the alkoxysilane include tetramethoxysilane and tetraethoxysilane.

본 발명에 사용할 수 있는 인화합물(알킬인산에스테르)로서는, 모노메틸인산에스테르, 모노에틸인산에스테르, 모노프로필인산에스테르, 모노부틸인산에스테르, 모노헥실인산에스테르, 모노옥틸인산에스테르, 모노데실인산에스테르, 디메틸인산에스테르, 디에틸인산에스테르, 디프로필인산에스테르, 디부틸인산에스테르, 디헥실인산에스테르, 디옥틸인산에스테르, 디데실인산에스테르, 트리메틸인산에스테르, 트리에틸인산에스테르, 트리프로필인산에스테르, 트리부틸인산에스테르, 트리헥실인산에스테르, 트리옥틸인산에스테르, 트리데실인산에스테르로부터 선택되는 1종이상의 알킬인산에스테르이 있다.Examples of the phosphorus compound (alkyl phosphate ester) that can be used in the present invention include monomethyl phosphate ester, monoethyl phosphate ester, monopropyl phosphate ester, monobutyl phosphate ester, monohexyl phosphate ester, monooctyl phosphate ester, monodecyl phosphate ester, Dimethyl Phosphate, Diethyl Phosphate, Dipropyl Phosphate, Dibutyl Phosphate, Dihexyl Phosphate, Dioctyl Phosphate, Didecyl Phosphate, Trimethyl Phosphate, Triethyl Phosphate, Tripropyl Phosphate, Tributyl Phosphate There is at least one alkyl phosphate ester selected from phosphate ester, trihexyl phosphate ester, trioctyl phosphate ester and tridecyl phosphate ester.

본 발명의 구성에 의하면, 동일종류의 인계화합물 및 실리콘화합물을 미리 함유시킨 전해액을 두루마리형의 콘덴서소자에 단순히 함침시키는 경우와 비교해서, 인계화합물 및 실리콘화합물을 소자중심부까지 용이하게 분포시키는 일이 가능하게 된다. 이 때문에, 전극박의 수화(水和)에 의한 정전용량의 저하나 수소가스발생의 정도를 보다한층 개선할 수 있으므로, 보다 신뢰성이 높은 콘덴서를 구성할 수 있다.According to the configuration of the present invention, it is easier to distribute the phosphorus compound and the silicon compound to the center of the element as compared to the case where the electrolyte containing the same kind of phosphorus compound and the silicon compound is impregnated in the roll type capacitor element simply. It becomes possible. For this reason, since the fall of the capacitance by the hydration of electrode foil, and the grade of hydrogen gas generation can be improved further, a more reliable capacitor | condenser can be comprised.

이에 대해, 인계화합물을 미리 함유시킨 전해액을 두루마리형의 콘덴서소자에 단순히 함침시킨다고하는 종래의 제조방법에 의하면, 인계첨가제 및 실리콘화합물이 소자중심부까지 충분히 퍼지지않아, 분포가 불균일하게 된다. 이 결과, 종래의 제조방법에 의한 전해콘덴서는 수화에 의한 전극박의 열악화를 발생한다.On the other hand, according to the conventional manufacturing method of simply impregnating an electrolytic solution containing a phosphorus compound in advance in a roll type capacitor element, the phosphorus additive and the silicon compound do not sufficiently spread to the center of the element, resulting in uneven distribution. As a result, the electrolytic capacitor by the conventional manufacturing method produces the deterioration of the electrode foil by hydration.

상기 인화합물 및 실리콘화합물의 세퍼레이터에의 부착량이 세퍼레이터의 단위중량당 5.0㎎/g미만에서는 수화열악화억제효과가 충분하지 않으므로 바람직하지 않다. 또, 부착량이 세퍼레이터의 단위중량당 50.0㎎/g을 초과하는 범위에 있어서는, 인계화합물이 지닌 소수성(疏水性)의 긴사슬알킬사슬의 영향에 의해, 세퍼레이터에의 전해액의 침투성이 저하하기 때문에, 콘덴서의 임피던스가 커져서 바람직하지 않다.If the adhesion amount of the phosphorus compound and the silicon compound to the separator is less than 5.0 mg / g per unit weight of the separator, the hydration deterioration inhibitory effect is not sufficient, which is not preferable. In addition, in the range where the adhesion amount exceeds 50.0 mg / g per unit weight of the separator, the permeability of the electrolyte solution to the separator is lowered due to the influence of the hydrophobic long chain alkyl chain of the phosphorus compound. It is not preferable because the impedance of the capacitor becomes large.

또, 상기 인화합물 및 실리콘화합물의 전극박에의 부착량이 전극박의 단위중량당 0.5㎎/g미만에서는 수화열악화억제효과가 충분하지 않으므로 바람직하지 않다. 또, 부착량이 전극박의 단위중량당 5.0㎎/g을 초과하는 범위에 있어서는, 전해액/전극박계면의 저항성분이 커져서, 콘덴서의 임피던스가 커지므로 바람직하지 않다. 음극박에 대해서는, 화성(化成), 미화성 어느경우도 마찬가지의 효과를 발현할 수 있으나, 더욱 신뢰성을 높이기위해서는, 음극에 1∼2V정도의 화성처리를 행하는 것이 바람직하다.Moreover, when the adhesion amount of the said phosphorus compound and a silicon compound to electrode foil is less than 0.5 mg / g per unit weight of electrode foil, since the hydration deterioration suppression effect is not enough, it is unpreferable. Moreover, in the range whose adhesion amount exceeds 5.0 mg / g per unit weight of electrode foil, since the resistance component of electrolyte solution / electrode foil interface becomes large and the impedance of a capacitor becomes large, it is unpreferable. In the case of the negative electrode foil, the same effect can be exhibited in both the chemical conversion and the fine chemical, but in order to further increase the reliability, it is preferable to perform chemical conversion treatment of about 1 to 2 V on the negative electrode.

본 발명의 봉구재로는 이소부틸렌이소프렌고무, 에틸렌프로필렌터폴리머 및 그들의 혼합물이 사용된다. 봉구재의 경도는 65∼100IRHD(국제고무경도단위)가 바람직하다. 봉구재의 경도가 65IRHD미만의 경우, 가스발생이 적은 콘덴서에 있어서도, 100℃를 넘는 온도에서, 콘덴서의 외관변형이 발생하거나, 봉구고무의 튀어나옴이 발생하거나 하므로 바람직하지 않다. 이것은, 전해액속에 함유되는 수분의 기화에 의한 것이다. 또, 경도가 100IRHD를 넘는 경우에 있어서는, 고무가 취약해져, 시험중에 고무에 균열이 생기는 등의 불편이 발생하므로 바람직하지 않다. 또, 실리콘화합물을 봉구재의 내부에 함유시키거나, 표면에 부착시켰을 경우, 특히 양극(陽極)리드의 부식반응을 억제할 수 있다. 또 전해액속의 용매의 증발을 억제할 수 있기 때문에 정전용량의 저하를 억제할 수 있다.As the sealing material of the present invention, isobutylene isoprene rubber, ethylene propylene terpolymer and mixtures thereof are used. The hardness of the sealing material is preferably 65 to 100 IRHD (International Rubber Hardness Unit). If the hardness of the sealing material is less than 65 IRHD, even in a capacitor with less gas generation, it is not preferable because the appearance deformation of the condenser occurs or the sealing rubber sticks out at a temperature exceeding 100 ° C. This is due to vaporization of moisture contained in the electrolyte solution. Moreover, when hardness exceeds 100 IRHD, rubber | gum becomes weak and it is unpreferable since inconvenience, such as a crack generate | occur | produces in rubber | gum, arises during a test. In addition, when the silicon compound is contained inside the sealing material or adhered to the surface, the corrosion reaction of the anode lead can be suppressed in particular. Moreover, since the evaporation of the solvent in electrolyte solution can be suppressed, the fall of a capacitance can be suppressed.

다음에 본 발명에 대해서 구체예를 들어서 설명한다.Next, the present invention will be described with reference to specific examples.

표 1에 본 발명의 실시형태 1∼25 및 비교예 1∼8에서 사용한 세퍼레이터의 인화합물 또는 실리콘화합물부착량, 사용한 전극박의 인화합물 또는 실리콘화합물부착량, 사용한 봉구재의 함유염소량, 봉구재의 경도 및 표면처리한 실리콘화합물, 알루미늄케이스의 바닥면 두께 및 알루미늄케이스내면에 처리를 행한 화합물을 표시한다.Table 1 shows the amount of phosphorus or silicon compound attached to the separator used in Embodiments 1 to 25 and Comparative Examples 1 to 8 of the present invention, the amount of phosphorus or silicon compound attached to the electrode foil used, the amount of chlorine contained in the used sealing material, the hardness and surface of the sealing material. The treated silicon compound, the thickness of the bottom surface of the aluminum case and the inner surface of the aluminum case are indicated.

봉구고무에는 경도(IRHD)70, 염소함유량 100ppm의 것을 사용했다. 비교를 위하여, 비교예 8로서, 세퍼레이터에 차아인산암모늄을 100㎎/g부착시킨 것도 시험했다.As the sealing rubber, one having a hardness (IRHD) of 70 and a chlorine content of 100 ppm was used. For comparison, as Comparative Example 8, 100 mg / g of ammonium hypophosphite adhered to the separator was also tested.

본 발명의 실시형태 1∼25의 전해액의 인화점을 클리블랜드개방식법에 의해 측정한 결과, 128℃∼134℃의 온도범위에 있어서 이들 전해액은 인화점을 지니지않았다. 또, 본 발명의 실시형태 1∼25의 전해액을 -30℃저온항온조속에서 24시간 방치한 결과, 전해액의 성상(性狀)변화는 확인되지 않았다. 이 실험에 의해, 전해액의 응고점이 -10℃이하인 것도 확인되었다.The flash point of the electrolyte solution of Embodiments 1-25 of this invention was measured by the Cleveland opening method, As a result, these electrolyte solution did not have a flash point in the temperature range of 128 degreeC-134 degreeC. Moreover, when the electrolyte solution of Embodiments 1-25 of this invention was left to stand for 24 hours in -30 degreeC low temperature thermostat, the change of the property of electrolyte solution was not confirmed. This experiment also confirmed that the solidification point of the electrolyte solution was -10 ° C or lower.

또한, 표 1에 기재의 화합물7∼화합물14의 화학식은 별지에 표시한다.In addition, the chemical formulas of the compounds 7 to 14 shown in Table 1 are shown in separate sheets.

표 2∼표 5에 본 발명의 실시형태 1∼25 및 비교예 1∼8의 전해액을 사용해서 구성한 전해콘덴서의 20℃/100㎑에 있어서의 임피던스에 대한 -10℃/100㎑의 임피던스비, 온도 110℃에서 1000시간의 정격전압인가 및 무부하방치시험후의 제품바닥면부의 팽창량, 누설전류의 변화율, 봉구고무로부터 투과된 용매의 투과량, 양극알루미늄리드의 부식성 및 봉구고무의 상태를 표시한다. 또한, 본시험에 제공한 알루미늄전해콘덴서는, 정격전압 6.3V-정전용량560μF(사이즈:ø8×11L) 및 정격전압 50V-정전용량 1500μF(사이즈:ø16×35.5L)의 2종류이다.Impedance ratio of -10 degreeC / 100 Hz with respect to the impedance in 20 degreeC / 100 Hz of the electrolytic capacitor comprised using the electrolyte solution of Embodiments 1-25 and Comparative Examples 1-8 of Table 2-Table 5, The expansion of the bottom surface of the product, the rate of change of leakage current, the amount of solvent permeated from the sealing rubber, the corrosiveness of the anode aluminum lead, and the sealing rubber after the rated voltage for 1000 hours at 110 ° C and no load unloading test. The aluminum electrolytic capacitors provided in this test are of two types: rated voltage of 6.3 V-capacitance 560 μF (size: ø8 x 11 L) and rated voltage of 50 V-capacitance of 1500 μF (size: ø16 x 35.5 L).

또, 세퍼레이터(마닐라삼섬유재질), 전극박 및 봉구고무(수지가황한 이소부틸렌이소프로필렌고무[부틸고무])의 인화합물 또는 실리콘화합물의 부착처리에 대해서는, 임의농도의 인화합물 또는 실리콘화합물의 수용액속에 세퍼레이터, 전극박 및 봉구고무를 침지처리한 후, 100℃속에서 1시간 건조처리를 행하였다. 또, 봉구고무속의 염소량에 대해서는, 일본국, 미쯔비시화학(주)제의 전(全)염소분석장치(물품번호: TS×10)에 의해 측정을 행하여, 봉구고무의 중량당의 염소량으로 환산해서 표시했다.In addition, phosphorus compounds or silicone compounds of any concentration for the adhesion treatment of the phosphorus compound or the silicon compound of the separator (manila hemp fiber material), electrode foil and sealing rubber (resin vulcanized isobutylene isopropylene rubber [butyl rubber]) The separator, electrode foil, and sealing rubber were immersed in an aqueous solution of, and then dried at 100 ° C. for 1 hour. In addition, the amount of chlorine in the sealing rubber is measured by a total chlorine analyzer (product number: TS × 10) manufactured by Mitsubishi Chemical Co., Ltd. in Japan, and converted into the amount of chlorine per weight of the sealing rubber. did.

표 2∼표 5의 결과로부터, 본 발명의 알루미늄전해콘덴서는, 임피던스비도 낮고, 110℃속의 수명시험에 있어서도 알루미늄케이스의 바닥면부의 팽창량(L치변화) 및 누설전류치의 변화율이 적고, 또한 양극알루미늄리드의 부식성, 봉구고무의 튀어나옴도 없는 것을 알 수 있다.From the results of Tables 2 to 5, the aluminum electrolytic capacitor of the present invention has a low impedance ratio, a small rate of change in the amount of expansion (L value change) and a leakage current value at the bottom of the aluminum case even in a life test at 110 ° C. It can be seen that there is no corrosion of anodized aluminum lead or sticking out of sealing rubber.

이상과 같이 본 발명의 전해콘덴서는, 20℃, 100㎑에 있어서의 임피던스에대한 -10℃, 100㎑의 임피던스비가 4이하이고, 또한 온도 100℃이상에서의 정격전압인가 및 무부하방치시험 1000시간에서의 알루미늄케이스의 바닥면부분의 밸브팽창량이 +1㎜이하이다. 또, 초기누설전류치에 대한 100℃이상에서의 무부하방치시험 1000시간이내에서의 누설전류치의 비율이 +5000%이하라는 성능을 지니고, 고온하에서 장시간 사용했을 경우에도 외관변화, 특성열악화가 적다. 또 전해액은 저온특성에 뛰어나고, 고함수율이기 때문에, 전자기기의 이상작동 등에 의해 알루미늄전해콘덴서에 이상 전압이나 역전압이 인가되어서 안전밸브가 작동하고, 전해액이 분출했을 때에도 발화의 위험성도 적다. 이 때문에, 본 발명에 의해, 신뢰성이 높은, 임피던스성능 및 저온특성에 뛰어난 정격전압 100V이하의 알루미늄전해콘덴서를 구성할 수 있다.As described above, the electrolytic capacitor of the present invention has an impedance ratio of -10 ° C and 100 mA to an impedance at 20 ° C and 100 mA of 4 or less, and a rated voltage at a temperature of 100 ° C or more and 1000 hours of unloading test. The valve expansion amount of the bottom part of the aluminum casing at +1 mm or less. Moreover, the ratio of the leakage current value within 1000 hours to the initial leakage current value at 100 ° C or more to the initial leakage current value is less than + 5000%, and there is little change in appearance and deterioration even when used for a long time at high temperature. In addition, since the electrolyte has excellent low temperature characteristics and a high water content, the safety valve operates because an abnormal voltage or reverse voltage is applied to the aluminum electrolytic capacitor due to abnormal operation of the electronic device, and the risk of ignition is small even when the electrolyte is ejected. Therefore, according to the present invention, an aluminum electrolytic capacitor having a rated voltage of 100 V or less, which is highly reliable, has excellent impedance performance and low temperature characteristics.

[화합물 7][Compound 7]

[화합물8][Compound 8]

[화합물9][Compound 9]

[화합물10][Compound 10]

[화합물11]Compound 11

[화합물12]Compound 12

[화합물13]Compound 13

[화합물14]Compound 14

Claims (17)

구동용 전해액의 함수율이 20∼90wt%이고, 또한 상기 구동용 전해액이 포름산암모늄, 아세트산암모늄, 락트산암모늄, 글리콜산암모늄, 옥살산암모늄, 숙신산암모늄, 말론산암모늄, 아디프산암모늄, 벤조산암모늄, 글루타르산암모늄, 아젤라산암모늄으로부터 선택되는 1종이상의 화합물을 주전해질로서 함유하고, 또한 트리메틸아디프산, 1,6-데칸디카르복시산, 세바스산, 1,7-옥탄디카르복시산, 부틸옥탄디카르복시산, 3-tert-부틸아디프산, 3-tert-옥틸헥산2산, 3-n-도데실헥산2산, 구조식 1로 표시되는 유기카르복시산, 구조식2로 표시되는 유기카르복시산 또는 이들 카르복시산의 암모늄염으로부터 선택되는 1종이상의 화합물을 1wt%이상함유한 것을 특징으로 하는 알루미늄전해콘덴서.The water content of the driving electrolyte is 20 to 90 wt%, and the driving electrolyte is ammonium formate, ammonium acetate, ammonium lactate, ammonium glycolate, ammonium oxalate, ammonium succinate, ammonium malonate, ammonium adipic acid, ammonium benzoate or glue. It contains at least one compound selected from ammonium tartrate and ammonium azelaate as the main electrolyte, and also trimethyladipic acid, 1,6-decanedicarboxylic acid, sebacic acid, 1,7-octanedicarboxylic acid, butyloctanedicarboxylic acid , 3-tert-butyladipic acid, 3-tert-octylhexanoic acid, 3-n-dodecylhexanoic acid, an organic carboxylic acid represented by formula 1, an organic carboxylic acid represented by formula 2, or an ammonium salt of these carboxylic acids An aluminum electrolytic capacitor, characterized by containing 1 wt% or more of at least one compound selected. 구조식 1 Structural Formula 1 단, R2는 저급알킬기, R1는 수소원자, 또는 다음의 기Provided that R 2 is a lower alkyl group, R 1 is a hydrogen atom, or 구조식 2 Structural Formula 2 단, R3, R4는 저급알킬기, R5는 페닐기.With the proviso that R 3 and R 4 are lower alkyl groups and R 5 is a phenyl group. 제 1항에 있어서, 상기 주전해질과, 상기 유기카르복시산, 또는 이들의 암모늄염으로부터 선택되는 1종이상의 화합물과의 함유량의 비율이 0.05이상∼5.0미만의 범위에 있고, 또한 상기 주전해질과, 상기 유기카르복시산, 또는 이들의 암모늄염으로부터 선택되는 1종이상의 화합물의 총함유량이 전해액의 중량에 대해서 10wt%이상인 구동용 전해액을 사용한 것을 특징으로 하는 알루미늄전해콘덴서.The content of the main electrolyte and the organic carboxylic acid or at least one compound selected from the ammonium salts thereof is in the range of 0.05 or more and less than 5.0, and the main electrolyte and the organic An aluminum electrolytic capacitor, wherein a driving electrolyte is used in which the total content of at least one compound selected from carboxylic acids or ammonium salts thereof is 10 wt% or more based on the weight of the electrolyte. 제 1항에 있어서, 상기 구동용전해액이, 다가알콜, 폴리글리세린, 폴리에틸렌글리콜, 에틸렌옥사이드와 프로필렌옥사이드로이루어진 공중합물로부터 선택되는 1종이상으로 이루어진 유기용매를 함유하고, 또한 알킬인산에스테르, 차아인산, 피로인산 및 이들의 염으로부터 선택되는 1종이상의 인화합물을 0.01wt%이상함유하고, 또한 p-니트로페놀, m-니트로페놀, o-니트로페놀, p-니트로벤조산, m-니트로벤조산, o-니트로벤조산, p-니트로아니솔, m-니트로아니솔, o-니트로아니솔로부터 선택되는 1종이상의 니트로화합물을 0.01wt%이상 함유하는 것임을 특징으로 하는 알루미늄전해콘덴서.2. The driving electrolyte according to claim 1, wherein the driving electrolyte contains one or more organic solvents selected from polyhydric alcohols, polyglycerols, polyethylene glycols, copolymers of ethylene oxide and propylene oxide, and also alkyl phosphate esters and teas. Containing at least 0.01 wt% of at least one phosphorus compound selected from phosphorous acid, pyrophosphoric acid and salts thereof, and also contains p-nitrophenol, m-nitrophenol, o-nitrophenol, p-nitrobenzoic acid, m-nitrobenzoic acid, An aluminum electrolytic capacitor, characterized in that it contains 0.01 wt% or more of one or more nitro compounds selected from o-nitrobenzoic acid, p-nitroanisole, m-nitroanisole, and o-nitroanisole. 제 3항에 있어서, 상기 알킬인산에스테르가 모노알킬인산에스테르, 디알킬인산에스테르, 트리알킬인산에스테르로부터 선택되는 1종이상의 화합물로서, 1분자당의 알킬사슬의 총탄소수가 3∼36개인 것을 특징으로 하는 알루미늄전해콘덴서.4. The alkyl phosphate ester according to claim 3, wherein the alkyl phosphate ester is at least one compound selected from monoalkyl phosphate esters, dialkyl phosphate esters and trialkyl phosphate esters, wherein the alkyl chains per molecule have 3 to 36 carbon atoms. Aluminum electrolytic capacitor 제 4항에 있어서, 상기 알킬인산에스테르가 모노메틸인산에스테르, 모노에틸인산에스테르, 모노프로필인산에스테르, 모노부틸인산에스테르, 모노헥실인산에스테르, 모노옥틸인산에스테르, 모노데실인산에스테르, 디메틸인산에스테르, 디에틸인산에스테르, 디프로필인산에스테르, 디부틸인산에스테르, 디헥실인산에스테르, 디옥틸인산에스테르, 디데실인산에스테르, 트리메틸인산에스테르, 트리에틸인산에스테르, 트리프로필인산에스테르, 트리부틸인산에스테르, 트리헥실인산에스테르, 트리옥틸인산에스테르, 트리데실인산에스테르로부터 선택되는 1종이상의 화합물인 것을 특징으로 하는 알루미늄전해콘덴서.The method of claim 4, wherein the alkyl phosphate ester is monomethyl phosphate ester, monoethyl phosphate ester, monopropyl phosphate ester, monobutyl phosphate ester, monohexyl phosphate ester, monooctyl phosphate ester, monodecyl phosphate ester, dimethyl phosphate ester, Diethyl Phosphate, Dipropyl Phosphate, Dibutyl Phosphate, Dihexyl Phosphate, Dioctyl Phosphate, Didecyl Phosphate, Trimethyl Phosphate, Triethyl Phosphate, Tripropyl Phosphate, Tributyl Phosphate, Tri An aluminum electrolytic capacitor, characterized in that at least one compound selected from hexyl phosphate ester, trioctyl phosphate ester, and tridecyl phosphate ester. 세퍼레이터에 알킬인산에스테르, 차아인산, 프로인산 또는 그들의 염 및 하기구조식으로 표시되는 실리콘화합물, 실란커플링제, 또는 알콕시실란으로부터 선택되는 1종이상의 화합물을 부착시킨 것을 특징으로 하는 알루미늄전해콘덴서.An aluminum electrolytic capacitor characterized by adhering one or more compounds selected from alkyl phosphate esters, hypophosphorous acid, prophosphoric acid or salts thereof, and silicone compounds, silane coupling agents, or alkoxysilanes represented by the following structural formulas to the separator. 단, X1, X5, X6은 알킬기, 알케닐기, 알릴기, 아랄킬기, X2, X3, X4는 알킬옥시기 또는 수산기.Provided that X 1 , X 5 and X 6 are alkyl groups, alkenyl groups, allyl groups, aralkyl groups, X 2 , X 3 and X 4 are alkyloxy groups or hydroxyl groups. 제 6항에 있어서, 상기 화합물의 부착량이 세퍼레이터의 단위중량당 5.0∼50.0㎎/g인 것을 특징으로 하는 알루미늄전해콘덴서.7. The aluminum electrolytic capacitor according to claim 6, wherein the adhesion amount of the compound is 5.0 to 50.0 mg / g per unit weight of the separator. 알루미늄박, 음극알루미늄박의 적어도 한쪽에 알킬인산에스테르, 차아인산, 피로인산 또는 그들의 염, 하기구조식으로 표시되는 실리콘화합물, 알콕시실란으로부터 선택되는 1종이상의 화합물을 부착시킨 것을 특징으로 하는 알루미늄전해콘덴서.An aluminum electrolytic capacitor, comprising at least one of aluminum foil and cathode aluminum foil attached with at least one compound selected from alkyl phosphate esters, hypophosphorous acid, pyrophosphoric acid or salts thereof, silicone compounds represented by the following structural formulas, and alkoxysilanes. . 단, X1, X5, X6은 알킬기, 알케니릭, 알릴기, 아랄킬기, X2, X3, X4는 알킬옥시기 또는 수산기.Provided that X 1 , X 5 and X 6 are alkyl groups, alkenic, allyl groups, aralkyl groups, X 2 , X 3 and X 4 are alkyloxy groups or hydroxyl groups. 제 8항에 있어서, 상기 화합물의 부착량이 전극박의 단위중량당 0.5∼5.0㎎/g인 것을 특징으로 하는 알루미늄전해콘덴서.9. The aluminum electrolytic capacitor according to claim 8, wherein the adhesion amount of the compound is 0.5 to 5.0 mg / g per unit weight of the electrode foil. 제 1항에 있어서, 봉구재가 이소부틸렌이소프렌고무, 에틸렌프로필렌터폴리머 및 그들의 혼합물로 이루어지고, 또한 봉구재의 경도가 65∼100IRHD(국제고무경도단위)인 것을 특징으로 하는 알루미늄전해콘덴서.The aluminum electrolytic capacitor according to claim 1, wherein the sealing material is composed of isobutylene isoprene rubber, ethylene propylene terpolymer and mixtures thereof, and the sealing material has a hardness of 65 to 100 IRHD (International Rubber Hardness Unit). 제 10항에 있어서, 봉구재의 함유염소량이 봉구재중량에 대해서 300ppm이하인 것을 특징으로 하는 알루미늄전해콘덴서.The aluminum electrolytic capacitor according to claim 10, wherein the chlorine content of the sealing material is 300 ppm or less with respect to the weight of the sealing material. 제 10항에 있어서, 하기구조식으로 표시되는 실리콘화합물, 실란커플링제, 알콕시실란으로부터 선택되는 1종이상의 화합물을 봉구재의 내부에 함유시키거나, 또는 표면에 부착시킨 것을 특징으로 하는 알루미늄전해콘덴서.The aluminum electrolytic capacitor according to claim 10, wherein at least one compound selected from silicone compounds, silane coupling agents, and alkoxysilanes represented by the following structural formulas is contained in the interior of the sealing material or adhered to the surface. 단, X1, X5, X6은 알킬기, 알케닐기, 알릴기, 아랄킬기, X2, X3, X4는 알킬옥시기 또는 수산기.Provided that X 1 , X 5 and X 6 are alkyl groups, alkenyl groups, allyl groups, aralkyl groups, X 2 , X 3 and X 4 are alkyloxy groups or hydroxyl groups. 알루미늄케이스의 내면에 알킬인산에스테르, 차아인산, 피로인산 또는 그들의 염, 또는 하기구조식으로 표시되는 실리콘화합물, 실란커플링제, 또는 알콕시실란으로부터 선택되는 1종이상의 화합물을 부착시킨 것을 특징으로 하는 알루미늄전해콘덴서.An aluminum electrolyte comprising an alkyl phosphate ester, hypophosphorous acid, pyrophosphoric acid or salts thereof, or at least one compound selected from a silicone compound, a silane coupling agent, or an alkoxysilane represented by the following structural formula attached to an inner surface of an aluminum case. Condenser. 단, X1, X5, X6은 알킬기, 알케닐기, 알릴기, 아랄킬기, X2, X3, X4는 알킬옥시기 또는 수산기.Provided that X 1 , X 5 and X 6 are alkyl groups, alkenyl groups, allyl groups, aralkyl groups, X 2 , X 3 and X 4 are alkyloxy groups or hydroxyl groups. 제 1항에 있어서, 상기 구동용전해액의 응고점이 -10℃이하인 것을 특징으로 하는 알루미늄전해콘덴서.The aluminum electrolytic capacitor according to claim 1, wherein the solidification point of the driving electrolyte is -10 deg. 제 1항에 있어서, 20℃, 100㎑에 있어서의 임피던스에 대한 -10℃, 100㎑의 임피던스비가 4이하인 정격전압 100v이하의 알루미늄 전해콘덴서.The aluminum electrolytic capacitor according to claim 1, wherein an impedance ratio of -10 ° C and 100 Hz to an impedance at 20 ° C and 100 Hz is 4 or less. 제 1항에 있어서, 온도 100℃이상에서의 정격전압부하 및 무부하방치시험에 있어서의 1000시간이내의 알루미늄케이스바닥면부분의 밸브팽장량이 +1㎜이내이고, 또한 초기누설전류치에 대한 100℃이상에서 무부하방치시험을 실시한 1000시간이내에서의 누설전류치의 변화율이 +5000%이내인 것을 특징으로 하는 알루미늄전해콘덴서.The valve expansion amount of the bottom part of the aluminum case within 1000 hours in the rated voltage load and no load leaving test at a temperature of 100 ° C. or higher is within +1 mm, and 100 ° C. with respect to the initial leakage current value. The aluminum electrolytic capacitor, characterized in that the rate of change of the leakage current value within 1000 hours after the no-load stand-by test is within + 5000%. 제 1항∼제 10항의 어느 한 항에 있어서, 알루미늄케이스가 알루미늄 또는 알루미늄합금으로 이루어지고 또한 알루미늄케이스바닥면부분의 판두께가 0.30㎜이상인 것을 특징으로 하는 알루미늄전해콘덴서.The aluminum electrolytic capacitor according to any one of claims 1 to 10, wherein the aluminum case is made of aluminum or an aluminum alloy, and the plate thickness of the bottom portion of the aluminum case is 0.30 mm or more.
KR10-1999-0044421A 1998-10-13 1999-10-13 aluminium electrolytic condenser KR100423196B1 (en)

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TW434603B (en) 2001-05-16
CN100426433C (en) 2008-10-15
DE69929023T2 (en) 2006-08-17
CN1607621A (en) 2005-04-20
EP0996134B1 (en) 2005-12-21
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MY123033A (en) 2006-05-31
CN1607618A (en) 2005-04-20

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